Polymeric stannoic acid products



United States Patent ,413,264 POLYMERIC STANNOI'C ACID PRODUCTS IngenuiuHechenbleikner, Kenwood, Raymond S. Dalter,

Cincinnati, and John F. Hussar, Loveland, Ohio, assignors to CarlisleChemical Works, Inc., Reading, Ohio, a corporation of Ohio No Drawing.Continuation-impart of application Ser. No. 427,487, July 22, 1965. Thisapplication July 13, 1965, Ser. No. 471,718

13 Claims. (Cl. 260-45.75)

ABSTRACT OF THE DISCLOSURE wherein R is hydrogen or methyl, R ishydrocarbyl, R is hydrogen or hydrocarbyl, m is 0 or a positive integerand q is an integer of at least 1.

This application is a continuation-in-part of application of Ser. No.427,487 filed Jan. 22, 1965.

This invention relates to novel polymeric stannoic acid derivatives.

It is an object of the present invention to prepare novel polymericstannoic acid derivatives.

Another object is to stabilize halogen containing vinyl resins.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by preparingcompounds having one of the formulae or a compound which may have theformula ice where R, and R are alkyl, aryl, aralkyl, alkenyl oralicyclic, R is n is an integer of at least 2 and can be 20 or more;

m is zero or a positive integer, usually not over 10;

R is hydrogen or hydrocarbyl, e.g. alkyl, alkenyl or phenyl;

R is hydrogen or methyl; and

q is an integer of at least 1.

The compounds of Formulae l, 2, 3, and 4 are prepared by thecondensation reaction of a hydrocarbyl stannoic acid with an equimolaramount of hydroxycarboxylic acid, a hydrocarbyl mercaptoalkanoate, or ahydrocarbyl half ester of an alkanedioic acid or of an alkenedioic acid.Water is split out as by product in the polymerization reaction and isremoved, preferably by azeotropic distillation, e.g. using a hydrocarbonsuch as benzene, toluene, xylene, hexane, heptane, octane or petroleumether as the aze-otroping agent.

The compounds which may have FOrmula'S are formed in similar fashion byreacting 1 mole of the hydrocarbyl stannoic acid with 2 moles of amonocarboxylic acid, a hydroxycarboxylic acid, a hydrocarbylmercaptoalkanoate, or a hydrocarbyl half ester of an alkanedioic acid oran alkenedioic acid. Desirably a slight excess over the 2 moles of the,carboxyl or mercapto group containing Q reactant is employed, e.g. up to2.5 moles of'such reactant per mole of stannoic acid.

As starting stannoic acids there can be used methyl stannoic acid,propyl stannoic acid, butyl stannoic acid, isobutyl stannoic acid, octylstannoic acid, dodecyl stannoic acid, 2-ethylhexyl stannoic acid, allylstannoic acid, vinyl stannoic acid, cyclohexyl stannoic acid,cyclopentyl stannoic acid, phenyl stannoic acid, o-tolyl stannoic acid,m-tolyl stannoic acid, p-tolyl stannoic acid, p-butylphenyl stannoicacid, benzyl stannoic acid, octadecyl stannoic acid and oleyl stannoicacid.

As hydrocarboxylic acids there can be used glycolic acid, lactic acid,fl-hydroxypropionic, and 'y-hydroxybutyric acid.

As hydrocarbyl mercaptoalkanoates there can be employed isooctylmercaptoacetate, octyl mercaptoacetate, isooctyl fi-mercaptopropionate,methyl mercaptoacetate, ethyl mercaptoacetate, butyl mercaptoacetate,hexyl mercaptoacetate, decyl mercaptoacetate, dodecyl mercaptoacetate,octadecyl mercaptoacetate, oleyl mercaptoacetate, allyl mercaptoacetate,benzyl mercaptoacetate, cyclohexylmercaptoacetate, phenylmercaptoacetate, p-tolyl mercaptoacetate, o-tolyl mercaptoacetate,m-tolyl mercaptoacetate, p-butylphenyl mercaptoacetate, cyclopentylmercaptoacetate, Z-ethylhexyl mercaptoacetate, butyl B-mercaptopropionate, phenyl fl-mercaptoproprionate, allyl 5mercaptopropionate, dodecyl B mercaptopropionate, cyclophenylfl-mercaptopropionate, benzyl B-mercaptopropionate, octyl;3-mercaptopropionate, methyl fl-mercaptopropionate, ethylB-mercaptopropionate, hexyl B- mercaptopropionate, isodecylfl-mercaptopropionate, octadecyl fl-mercaptopropionate, oleyl,B-mercaptopropionate p-tolyl S-mercaptopropionate, o-tolylfi-mercaptopropionate, p-butylphenyl fl-mercaptopropionate Z-ethylhexylfimercaptopropionate and octyl -mercaptobutylrate.

As hydrocarbyl half esters of alkane or alkene dioic acids there can beused mono octyl oxalate, mono butyl malonate, mono methyl succinate,mono butyl maleate, mono ethyl fumarate, mono butyl glutarate, monopropyl adipate, mono isooctyl succinate, mono methyl sebacate, monophenyl succinate, mono benzyl malonate, mono cyclohexyl adipate, monooctadecyl azelate, mono ally succinate, mono oleyl glutarate.

As monocarboxylic acids there can be used acetic acid, propionic acid,butyric acid, valeric acid, decanoic acid, palmitic acid, stearic acid,oleic acid, acrylic acid, benzoic acid, o-toluic acid, p-toluic acid,m-toluic acid and cyclohexane carboxylic acid.

Illustrative of compounds of the present invention within Formula 1 madeby the use of equimolar amounts of the stannoic acid and hydroxycarboxylic acids are the condensation product of butyl stannoic acidwith either glycolic acid or lactic acid or B-hydroxypropionic acid or-hydroxybutyric acid. The condensation product of octyl stannoic acidwith glycolic acid or lactic acid or B-hydroxypropionic acid, thecondensation product of dodecyl stannoic acid with glycolic acid, thecondensation product of dodecyl stannoic acid with glycolic acid, thecondensation product of methyl stannoic acid with lactic acid, thecondensation product of phenyl stannoic acid with glycolic acid, thecondensation product of allyl stannoic acid with B-hydroxypropionicacid, the condensation product of benzyl stannoic acid with glycolicacid, the condensation product of cyclohexyl stannoic acid with lacticacid.

Illustrative of compounds of the present invention within Formula 2 madeby the use of equimolar amounts of the stannoic acid and hydrocarbylmercaptoalkanoates captopropionate or allyl p-mercaptopropionate, or do-4 decyl fi-mercaptopropionate, or benzyl B-mercaptopropionate, or octyl'y-mercaptobutyrate; the condensation products of methyl stannoic acidwith isooctyl mercaptoacetate, or octyl B-mercaptopropionate; thecondensation products of octyl stannoic acid with isooctylmercaptoacetate, or isooctyl ,S-mercaptopropionate, or methylmercaptoacetate, or isodecyl mercaptoacetate, or benzylfi-mercaptopropionate, or phenyl mercaptoacetate, or cyclohexylB-mercaptopropionate, or oleyl mercaptoacetate; or hexylfi-mercaptopropionate, or methyl fi-mercaptopropionate, or ethylB-mercaptopropionate, or isodecyl B-rnercaptopropionate or octadecylfi-mercaptopropionate, or oleyl fl-mercaptopropionate, or p-tolyl 3-mercaptopropionate, or o-tolyl fl-mercaptopropionate, or p-butylphenylp-mercaptopropionate, or Z-ethylhexyl B- mercaptopropionate; thecondensation products of isobutyl stannoic acid with propylmercaptoacetate, or amyl fi-mercaptopropionate, the condensationproducts of 2- ethyl hexyl stannoic acid with heptyl mercaptoacetate orp-tolyl fi-mercaptopropionate; the condensation product of allylstannoic acid with isooctyl mercaptoacetate; the condensation product ofoleyl stannoic acid with propyl fl-mercaptopropionate; the condensationproducts of cyclohexyl stannoic acid with nonyl mercaptoacetate orisooctyl B-mercaptopropionate; the condensation products of phenylstannoic acid with butyl mercaptoacetate, or decylfl-mercaptopropionate, or phenyl mercaptoacetate; or phenylB-mercaptopropionate; the condensation product of benzyl stannoic acidwith hexyl mercaptoacetate or isooctyl p-inercaptopropionate; thecondensation product of octadecyl stannoic acid with ethylmercaptoacetate or butyl fl-mercaptopropionate.

Illustrative of compounds of the present invention within Formulae 3 and4 made by the use of equirnolar amounts of the stannoic acid and halfesters of dicarboxylic acids are the condensation products of butylstannoic acid with mono octyl oxalate, or mono butyl malonate, or monomethyl succinate, or mono butyl maleate, or mono ethyl fumarate, or monobutyl glutarate, or mono propyl adipate, or mono isooctyl succinate, ormono methyl sebacate, or mono phenyl succinate, or mono benzyl malonate,or mono cyclohexyl adipate, or mono octadecyl azelate, or mono allylsuccinate, or mono oleyl glutarate; the condensation products of methylstannoic acid with mono octyl oxalate, or mono butyl malonate, or monomethyl succinate, or mono ethyl maleate, or mono isooctyl adipate; thecondensation products of octyl stannoic acid with mono amyl oxalate, ormono hexyl malonate, or mono butyl succinate, or mono octyl maleate, ormono isobutyl fumarate, or mono phenyl adipate, or mono cyclohexylsebacate; the condensation products of isobutyl stannoic acid with monoheptyl succinate or mono benzyl pimelate; the condensation products of2-ethylhexyl stannoic acid with mono butyl malonate, or mono p-tolylsuccinate; the condensation product of oleyl stannoic acid with monohexyl adipate; the condensation products of cyclohexyl stannoic acidwith mono amyl adipate, or mono methyl succinate, or mono phenylglutarate; the condensation products of phenyl stannoic acid with monophenyl malonate, or mono ethyl fumarate, or mono butyl maleate, or monooctyl succinate; the condensation product of benzyl stannoic acid withmono butyl succinate; the condensation product of octadecyl stannoicacid with mono octyl malonate.

Illustrative of compounds of the present invention which may haveFormula 5 and are made by reacting 1 mole of the stannoic acid with 2moles of a mono carboxylic acid, a hydroxycarboxylic acid, a hydrocarbylmercaptoalkanoate, or a hydrocarbyl half ester of an alkane or alkenedioic acid are the reaction product of 1 mole of butyl stannoic acidwith 2 moles or a-hydroxy propionic acid; the reaction product of 1 moleof butyl stannoic acid with 2 moles of fi-hydroxypropionic acid; thereaction product of 1 mole of butyl stannoic acid with 2 moles orgamma-hydroxybutyric acid; the reaction product of 1 mole of octylstannoic acid with 2 moles of hydroxyacetic acid; the reaction productof 1 mole of octyl stannoic acid with 2 moles of a-hydroxpropionic acid;the reaction product of 1 mole of octyl stannoic acid with 2 moles ofgamma-hydroxybutyric acid; the reaction product of 1 mole of dodecylstannoic acid with 2 moles of hydroxyacetic acid; the reaction productof 1 mole of methyl stannoic acid with 2 moles of a-hyroxypropionicacid; the reaction product of 1 mole of phenyl stannoic acid with 2moles of hydroxyacetic acid; the reaction product of allyl stannoic acidwith 2 moles of fl-hydroxypropionic acid; the reaction product of 1 moleof benzyl stannoic acid with 2 moles of hydroxyacetic acid; the reactionproduct of 1 mole of cyclohexyl stannoic acid with 2 moles ofa-hydroxypropionic acid; the reaction product of 1 mole of butylstannoic acid with 2 moles of isooctyl mercaptoacetate; the reactionproduct of 1 mole of butyl stannoic acid with 2 moles of isooctyl,B-mercapto propionate; the reaction product of 1 mole of butyl stannoicacid with 2 moles of methyl mercaptoacetate; the reaction product of 1mole of butyl stannoic acid with 2 moles of ethyl mercaptoacetate; thereaction product of 1 mole of butyl stannoic acid with 2 moles of butylmercaptoacetate; the reaction product of 1 mole of butyl stannoic acidwith 2 moles of hexyl mercaptoacetate; the reaction product of 1 mole ofbutyl stannoic acid with 2 moles of decyl mercaptoacetate; the reactionproduct of 1 mole butyl stannoic acid with 2 moles of (lodecylmercaptoacetate; the reaction product 0t 1 mole of butyl stannoic acidwith 2 moles of octadecyl mercaptoacetate; the reaction product of 1mole of butyl stannoic acid with 2 moles of oleyl mercaptoacetate; thereaction product of 1 mole of butyl stannoic acid with 2 moles of allylmercaptoacetate; the reaction product of lmole of butyl stannoic acidwith 2 moles of benzyl mercaptoacetate; the reaction product of 1 moleof butyl stannoic acid with 2 moles of cyclohexyl mercaptoacetate; thereaction product of 1 mole of butyl stannoic acid with 2 moles of phenylmercaptoacetate; the reaction product of one mole of butyl stannoicacide with 2 moles of p-tolyl mercaptoacetate; the reaction product of 1mole of butyl stannoic acid with 2 moles of o-tolyl mercaptoacetate; thereaction product of 1 mole of butyl stannoic acid with 2 moles ofm-tolyl merca-ptoacetate; the reaction product of 1 mole of butylstannoic acid with 2 moles of p-butylphenyl mercaptoacetate; thereaction product of 1 mole of butyl stannoic acid with 2 moles of2-ethylhexyl mercaptoacetate; the reaction product of 1 mole of butylstannoic acid with 2 moles of butyl p-mercaptoprop-ionate; thereaction'product of 1 mole of butyl stannoic acid with'2 moles of phenylfi-mercaptopropionate; the reaction product of 1 mole of butyl stannoicacid with 2 moles of allyl fi-mercaptopropionate; the reaction productof 1 mole of butyl stannoic acid with 2 moles of dodecylfl-mercaptopropiomate; the reaction product of 1 mole of butyl stannoicacid with 2 moles of benzyl fl-mercaptopropionate; the reaction productof 1 mole of butyl stannoic acid with 2 moles of octyl gammamercaptobutyrate; the reaction product of 1 mole of methyl stannoic acidwith 2 moles of isooctyl mercaptoacetate; the reaction product of 1 moleof methyl stannoic acid with 2 moles of octyl fl-mercaptopropionate; thereaction product of 1 mole of octyl stannoic acid with 2 moles ofisooctyl merca-ptoacetate; the reaction product of 1 mole of octylstannoic acid with 2 moles of isooctyl fl-mercaptopropionate; thereaction product of 1 mole of octyl stannoic acid with 2 moles of methylmercaptoacetate; the reaction product of 1 mole of octyl stannoic acidwith 2 moles of isodecyl mercaptoacetate; the reaction product of 1 moleof octyl stannoic acid with 2 moles of benzyl fi-mercaptopropiomate; thereaction product of 1 mole of octyl stannoic acid with 2 moles of phenylmercaptoacetate; the reaction product of 1 mole of octyl stannoic acidwith 2 moles of cyclohexyl B-mercaptopropionate; the reaction product of1 mole of octyl stannoic acid with 2 moles of oleyl mercaptoacetatc; thereaction product of 1 mole of isobutyl stannoic acid with 2 moles ofpropyl mercaptoacetate; the reaction product of 1 mole of isobutyl stan-I n-oic acid with 2 moles of amyl B-mercaptopropionate; the reactionproduct of 1 mole of 2-ethylhexyl stannoic acid with 2 moles of heptylmercaptoacetate; the reaction product of 1 mole of 2-ethylhexyl stannoicacid with 2 moles of p-tolyl B-mercaptopropionate; the reaction productof 1 mole of allyl stannoic acid with 2 moles of isooctylmercaptoacetate; the reaction product of 1 mole of oleyl stannoic acidwith 2 moles of propyl fl-mercaptopropionate; the reaction product of 1mole of cyclohexyl stannoic acid with 2 moles of nonyl mercaptoacetate;the reaction product of 1 mole of cyclohexyl stannoic acid with 2 molesof isooctyl p-mercaptopropiomate; the reaction product of 1 mole ofphenyl stannoic acid with 2 moles of butyl mercaptoacetate; the reactionproduct of 1 mole of phenyl stannoic acid with 2 moles of decyl[i-mercaptoacetate; the reaction product of 1 mole of phenyl stannoicacid with 2 moles of phenyl mercaptoacetate; the reaction product of 1mole of benzyl stannoic acid with 2 moles of hexyl mercaptoacetate; thereaction product of 1 mole of octadecyl stannoic acid with 2 moles ofethyl mercaptoacetate; the reaction prod uct of 1 mole of butyl stannoicacid with 2 moles of monooctyl oxalate; the reaction product of 1 moleof butyl 2 moles of mono methyl succinate; the reaction product of 1mole of butyl stannoic acid with 2 moles of mono butyl maleate; thereaction product of 1 mole of butyl stannoic acid with 2 moles of monoethyl fumarate; the reaction product of 1 mole of butyl stannoic acidwith 2 moles of mono butyl glutarate; the reaction product of 1 mole ofbutyl stannoic acid with 2 moles of mono propyl adipate; the reactionproduct of 1 mole of butyl stannoic acid with 2 moles of mono isooctylsuccinate; the reaction product of 1 mole of butyl stannoic acid with 2moles of mono methyl sebacate; the reaction product of 1 mole of butylstannoic acid with 2 moles of mono phenyl succinate; the reactionproduct of 1 mole of butyl stannoic acid with 2 moles of mono benzylmalonate; the reaction product of 1 mole of butyl stannoic acid with 2moles of mono cyclohexyl adipate; the reaction product of 1 mole ofbutyl stannoic acid with 2 moles of mono octadecyl azelate; the reactionproduct of 1 mole of butyl stannoic acid with 2 moles of mono allylsuccinate; the reaction product of 1 mole of butyl stannoic acid with 2moles of mono oleyl glutarat'e; the reaction product of 1 mole of methylstannoic acid with 2 moles of mono octyl oxalate; the reaction productof 1 mole of methyl stannoic acid with 2 moles of mono butyl malonate;the reaction product of 1 mole of methyl stannoic acid with 2 moles ofmono methyl succinate; the reaction product of 1 mole of methyl stannoicacid with 2 moles of mono ethyl maleate; the reaction product of 1 moleof methyl stannoic acid with 2 moles of mono isooctyl adipate; thereaction product of 1 mole of octyl stannoic acid with 2 moles of monoamyl oxalate; the reaction product of 1 mole of octyl stannoic acid with2 moles of mono hexyl malonate; the reaction product of 1 mole ofoctylstannoic acid with 2 moles of mono butyl succinate; the reaction productof 1 mole of octyl stannoic acid with 2 moles of mono octyl maleate; thereaction product of 1 mole of octyl stannoic acid with 2 moles of monoisobutyl fumarate; the reaction product of 1 mole of octyl stannoic acidwith 2 moles of mono phenyl adipate; the reaction product of 1 mole ofoctyl stannoic acid with 2 moles of mono cyclohexyl sebacate; thereaction product of 1 mole of isobutyl stannoic acid with 2 moles ofmono heptyl succinate; the reaction product of 1 mole of benzyl stannoicacid with 2 moles of mono benzyl pimelate; the reaction product of 1mole of 2-ethylhexyl stannoic acid with 2 moles of mono butyl malonate;the reaction product of 1 mole of 2-ethylhexyl stannoic acid with 2moles of mono p-tolyl succinate; the reaction product of 1 mole of oleylstannoic acid with 2 moles of mono hexyl adipate; the reaction productof 1 mole of cyclohexyl stannoic acid with 2 moles of mono amyl adipate;the reaction product of 1 mole of cyclohexyl stannoic acid with 2 molesof mono methyl succinate; the reaction product of 1 mole of cyclohexylstannoic acid with 2 moles of mono phenyl glutarate; the reactionproduct of 1 mole of phenyl stannoic acid with 2 moles of mono phenylmalonate; the reaction product of 1 mole of phenyl stannoic acid with 2moles of mono ethyl fumarate; the reaction product of 1 mole of phenylstannoic acidwith 2 moles of mono butyl maleate; the reaction product of1 mole of phenyl stannoic acid with 2 moles of mono octyl succinate; thereaction product of 1 mole of benzyl stannoic acid with 2 moles of monobutyl succinate; the reaction product of 1 mole of octadecyl stannoicacid with 2 moles of monooctyl malonate; the reaction product of 1 moleof butyl stannoic acid with 2 moles of acetic acid; the reaction productof 1 mole of butyl stannoic acid with 2 moles of propionic acid; thereaction product of 1 mole of butyl stannoic acid with 2 moles of formicacid; the reaction product of 1 mole of butyl stannoic acid with 2 molesof butyric acid; the reaction product of 1 mole of butyl stannoic acidwith 2 moles of valeric acid; the reaction product of 1 mole of butylstannoic acid with 2 moles of decanoic acid; the reaction product of 1mole of butyl stannoic acid with 2 moles of cyclohaxanoic acid; thereaction of 1 mole of butyl stannoic acid with 2 moles of stearic cid;the reaction product of 1 mole of butyl stannoic acid' with 2 moles ofoleic acid; the reaction product of 1 mole of butyl stannoic acid with 2moles of arcylic acid; the reaction product of 1 mole of butyl stannoicacid with 2 moles of benzoic acid; the reaction product of 1 mole ofbutyl stannoic acid with 2 moles of o-toluic acid; the reaction productof 1 mole of butyl stannoic acid with 2 moles of p-toluic acid; thereaction product of 1 mole of butyl stannoic acid with 2 moles ofm-toluic acid; the reaction product of 1 mole of butyl stannoic acidwith 2 moles of cyclohexanoic acid; the reaction product of 1 mole ofmethyl stannoic acid with 2 moles of acetic acid; the reaction productof 1 mole of methyl stannoic acid with 2 moles of valeric acid; thereaction product of 1 mole of methyl stannoic acid with 2 moles ofbenzoic acid; the reaction product of 1 mole of octyl stannoic acid with2 moles of acetic acid; the reaction product of 1 mole of octyl stannoicacid with 2 moles of propionic acid; the reaction product of 1 mole ofoctyl stannoic acid with 2 moles of stearic acid; the reaction productof 1 mole of octyl stannoic acid with 2 moles of benzoic acid; thereaction product of 1 mole of phenyl stannoic acid with 2 moles ofbenzoic acid; the reaction product of 1 mole of phenyl stannoic acidwith 2 moles of acetic acid; and the reaction product of 1 mole ofphenyl stannoic acid with 2 moles of butyric acid In addition to thecompounds set forth above there can also be employed as stabilizers forhalogen containing resins compounds prepared by reacting a hydrocarbylstannoic acid with an equimolar amount of a hydrocarbyl mono carboxylicacid and a removal of water as previously set forth. Thus there can beused such condensation products of butyl stannoic acid with eitheracetic acid, or propionic acid, or butyric acid, or Valerie acid, ordecanoic acid, or palmitic acid, or stearic acid, or oleic acid, orformic acid, or acrylic acid, or benzoic acid, or o-toluic acid, orp-toluic acid, or m-toluic acid, or cyclohexane carboxylic acid; thecondensation products of methyl. stannoic acid with either acetic acidor valeric acid or benzoic acid; the condensation products of octylstannoic acid with either acetic acid, or propionic acid, or butyricacid, or stearic acid, or formic acid, or benzoic acid; the condensationproducts of phenyl stannoic acid with either acetic acid, or propionicacid, or palmitic acid or benzoic acid.

Surprisingly the tin containing mercaptopropionates are considerablysuperior to the corresponding tin containing mercaptoacetates asstabilizers. This has been observed not only in connection with thealkyltin mono(alkyl mercaptopropionates) and alkyltin di(alkylmercaptopropionates) but has even been observed with the alkyltintri(alkyl mercaptopropionates).

Thus while the Stefl Patent 2,731,482 shows that 3 moles of 2-ethylhexyl thioglycolate can be reacted with 1 mole of butyl stannic acid,column 5, lines 38 and 63 and column 6 lines 10-36 to prepare butyltintris(2-ethylhexyl mercaptoacetate) and that such products are useful asstabilizers for vinyl chloride resins, if 2-ethyl hexylfl-mercaptopropionate is used to prepare the corresponding butyltintri(2-ethylhexyl fi-mercaptopropionate) an even better vinyl chlorideresin stabilizer is prepared. Likewise monobutyltin tris(isooctylpmercaptopropionate) has been found superior to monobutyltintris(isooctyl thioglycolate) as a vinyl chloride resin stabilizer. Themonobutyltin tris(isooctyl B-mercaptopropionate) was prepared by theStefl general procedure cited supra. The monobutyltin tris(isooctylfi-mercaptopropionate) was also superior as a vinyl chloride resinstabilizer to dibutyltin bis (isooctyl thioglycolate).

Unless otherwise indicated all parts and percentages are by weight.

The stabilizers of the present invention can be used with halogencontaining vinyl and vinylidene resins in which the halogen is attacheddirectly to the carbon atoms.

Preferably, the resin is a vinyl halide resin, specifically, a vinylchloride resin. Usually, the vinyl chloride resin is made from monomersconsisting of vinyl chloride alone or a mixture of monomers comprisingat least 70% vinyl chloride by weight. When vinyl chloride copolymersare stabilized, preferably the copolymer of vinyl chloride with anethylenically unsaturated compound copolymerizable therewith contains atleast 10% of polymerized vinyl chloride.

As the chlorinated resin there can be employed chlorinated polyethylenehaving 14 to 75%, e.g. 27%, chlorine by weight, polyvinyl chloride,polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride,copolymers of vinyl chloride with 1 to preferably, 1 to 30%, of acopolymerizable ethylenically unsaturated material such as vinylacetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethylfumarate, diethyl maleate, other alkyl fumarates and maleates, vinylpropionate, methyl acrylate, Z-ethylhexyl acrylate, butyl acrylate andother alkyl acrylates, methyl methacrylate, ethyl methacrylate, butylmethacrylate and other alkyl methacrylates, methyl alpha chloroacrylate,styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether,vinyl chloroethyl ether and vinyl phenyl ether, vinyl ketones such asvinyl methyl ketone and vinyl phenyl ketone, l-fluoro-lchloroethylene,acrylonitrile, chloroacrylonitrile, allylidene diacetate andchloroallylidene diacetate. Typical copolymers include vinylchloride-vinyl acetate (96:4 sold commercially as VYNW), vinylchloride-vinylacetate (87:13), vinyl chloride-vinyl acetate-maleicanhydride (8611311), vinyl chloride-vinylidcne chloride (:5), vinylchloride-diethyl fumarate (95:5), vinyl chloride-trichloroethylene(95:5), vinyl chloride-Z-ethylhexyl acrylate (80:20).

The stabilizers of the present invention can be incorporated with theresin by admixing in an appropriate mill or mixer or by any of the otherwell-known methods which provide for uniform distribution throughout theresin compositions. Thus, mixing can be accomplished by milling on rollsat l00l60 C.

In addition to the novel stabilizers there can also be incorporated withthe resin conventional additives such as plasticizers, pigments,fillers, dyes, ultraviolet light absorbing agents, densifying agents andthe like.

If a plasticizer is employed, it is used in conventional amount, e.g. 30to 150 parts per 100 parts of resin. Typical plasticizers aredi-2-ethylhexyl phthalate, dibutyl sebacate, dioctyl sebacate, tricresylphosphate.

The tin containing stabilizers are normally used in an amount of 0.01 to10% by weight of the resin, more preferably 0.2 to 5% of the tincompound is used by weight of the resin.

There can also be included with the novel stabilizers of the presentinvention conventional stabilizers and antioxidants to assist inimproving the properties of the halo gen containing resin. Thus therecan be included 0.01- 10%, preferably 0.15% based on the resin of sulfurcontaining compounds such as dilauryl-thiodipropionate, distearyl 3,3thiodipropionate, dicyclohexyl-3,3'-thiodipropionate, dicetyl 3,3thiodipropionate, dioctyl 3,3- thiodipropionate, dibenzyl 3,3thiodipropionate, lauryl myristyl-3,3-thiodipropi0nate, diphenyl 3,3thiodipropionate, di-pmethoxyphenyl- 3,3-thiodipropionate, didecyl 3,3thiodipropionate, dibenzyl-3,3'-thiodipropio nate,diethyl-3,3'-thiopropionatc, lauryl ester of 3-methylmercaptopropionicacid, lauryl ester of 3-butyl-mercaptopropionic acid, lauryl ester of3-lauryl rnercaptopropionic acid, phenyl ester of 3-octylmercaptopropionic acid, phenyl ester of 3-octyl mercaptopropionic acid,lauryl ester of 3-phenyl mercaptopropionic acid, lauryl ester of3-benzyl mercaptopropionic acid, lauryl ester of 3-(pmethoxy) phenylmercaptopropionic acid, lauryl ester of 3-cyclohexyl mercaptopropionicacid, lauryl ester of 3-hydroxymethyl mercaptopropionic acid, myristylester of 3 11ydroxyethyl mercaptopropionic acid, octyl ester of3-methoxymethyl mercaptopropionic acid, dilauryl ester of 3carboxylmethyl mercaptopropionic acid, dilauryl ester of 3-carboxypropylmercaptopropionic acid, dilauryl- 4,7 dithiasebacate, dilauryl 4,7,8,1tetrathiotetradecandioate, dimyristyl-4,11-dithiatetradecandioate,lauryl- 3-benz0thiazyl mercaptopropionate. Preferably the esterifyingalcohol is an alkanol having 10 to 18 carbon atoms. Other esters of betathiocarboxylic acids set forth in Gribbins Patent 2,519,744 can also beused.

Other beta thiocarboxyli-c acids include stearyl (1, 2-dicarboethoxyethylthio) acetate, stearyl (1,2-dicarbolauryloxyethylthio) acetate or the like. Compounds of this typecan be made by addition of alkyl ester of mercaptoacetic acid to adialkyl ester of maleic acid. Similar beta thiocarboxyl compounds can beused which are made by addition of an RSH compound across the maleicester double bond and where R is alkyl, aryl, alkylcarboxyalkyl,arylcarboxyalkyl or aralkyl. Examples of such compounds aredecylthiodilauryl malate, phenylthiodioctyl malate, cetyl (1,Z-dicarboethoxyethylthio) propionate and benzylthiodimyristyl malate.

Similarly useful beta thiocarboxyl synergistic compounds can be preparedby addition of the RSH compounds as defined above across the double bondof dialkyl itaconates, citraconates, fumarates or trialkyl aconitates,e.g. the addition product of lauryl mercaptan with dibutyl itaconate,the addition product of the stearyl ester of mercaptoacetic acid withdilauryl itaconate, the addition product of butyl mercaptan withdilauryl citraconate, the addition product of lauryl mercaptan withtributyl aconitate, the additional product of the lauryl ester ofmercaptopropionic acid with triethyl aconitate, pentaerythritol tetra(mercaptoacetate), pentaerythritol tetra (fl-mercaptopropionate),acetate).

There can also be included 01-10%, preferably 0.1% by weight of thehalogen containing resin of metal salt stabilizers such as Groups I andII metal soaps, e.g. calcium stearate, calcium 2-ethylhexoate, calciumoctoate, calcium oleate, calcium ricinoleate, calcium myristate, calciumpalmitate, calcium laurate, barium laurate, barium stearate, magnesiumstearate, zinc stearate, cadmium laurate, cadmium octoate, cadmiumstearate and sodium stearate. Other metal salts can be used as leadstearate, lead silicate, aluminum stearate, etc.

There can also be added phenolic antioxidants in an amount of 0.01-%,preferably 0.15%. Examples of such phenols include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, propyl gallatc,4,4-thiobis(6-t-butyl-mcresol), 4,4-cyclohexylidene diphenol,2,5-di-t-amyl hydroquinone, 4,4'-butylidene bis(6-t-buty1-m-cresol),hydroquinone monobenzyl ether, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,6-butyl-4-decyloxy phenol, 2-tbutyl-4-dodecyloxy phenol,2-t-butyl-4-dodecyloxy phenol, 2-t-butyl-4-octadecyloxy phenol,4,4-methylene-bis(2,6- di-t-butyl phenol), p-amino phenol,N-lauryloxy-p-amino phenol, 4,4-thiobis(3-methyl-6-t-butyl phenol), bis[0- (1,1,3,3-tetramethyl butyl)phenol] sulfide, 4-acetyl-firesorcylicacid, A stage p-t-butylphenolformaldehyde resin,4-dodecyloxy-Z-hydroxybenzophenone, 3-hydroxy- 4-(phenylcarbonyl) phenylpalmitate, n-dodecyl ester of 3-hydroxy-4-(phenyl carbonyl)phenoxyacetic acid, and t-butyl phenol.

The use of epoxy compounds in an amount of 0.01-5% in the polymercompositions is also valuable. Examples of such epoxy compounds includeepoxidized soya bean oil, epoxidized lard oil, epoxidized olive oil,epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil,epoxidized corn oil, epoxidized tung oil, epoxidized cottonseed oil,epichlorhydrinbis-phenol A resins(epichlorhydrin-diphenylolpropaneresins), phenoxy-propylene oxide, butoxy-propylene oxide, epoxidizedneopentylene oleate, glycidyl epoxystearate, epoxidized u-olefins,epoxidized glycidyl soyate, dicyclopentadiene, dioxide, epoxidized butyltollate, styrene oxide, dipentene dioxide, glycidol,

1,1,l-trimethylolethane tri (mercaptovinyl cyclohexene dioxide, glycidylether of resorcinol,

glycidol ether of hydroquinone, glycidyl ether of 1,5-di- The organicphosphites contain one or more, up to atotal of three, aryl, alkyl,aralkyl and alkaryl groups, in any combination. The term trialkylaryl isinclusive of alkyl, aryl, alkaryl and aralkyl phosphites containing anyassortment of alkyl, aryl, alkaryl and aralkyl groups. Exemplary aretriphenyl phosphite, tricresyl phosphite, tri(dimethylphenyl) phosphite,tributyl phosphite, trioctyl phosphite, tridoecyl phosphite, octyldiphenyl phosphite, dioctyl phenyl phosphite, tri(octylphenyl)phosphite, tri (nonylphenyl) phosphite, tribenzyl phosphite, butyl,dicresyl phosphite, octyl di(octylphenyl) phosphite, tri(Z-ethyl-hexyl)phosphite, tritolyl phosphite, tri(2-cyclohexylphenyl) phosphite,tri-alpha-naphthyl phosphite, tri(phenylphenyl) phosphite, andtri(Z-phenylethyl) phosphite.

Of course there can also be incorporated 0.01-10% of conventionalorganometallic stabilizers such as the known organotin carboxylates andmercaptides to impart lubricity regulation as well as for improvedstabilization. Such materials include butyltin tris dodecyl mercaptide,dibutyltin dilaurate, dibutyltin didodecyl mercaptide, dianyhydro trisdibutylstannane diol, dihydrocarbontin salts of carboxy mercaptals suchas those set forth in Hechenbleikner et al. Patent 3,078,290, dibutyltinbis(isooctylthioglycolate), etc. There can be included any of the vinylchloride resin stabilizers set forth in Salyer Patent 2,985,617.

Likewise there can be included polyol stabilizers for vinyl chlorideresins in an amount of 0.01-10%. Thus there can be included glycerol,sorbitol, pentaerythritol and mannitol.

Nitrogen containing stabilizers such as dicyandiam'ide, melamine, urea,formoguanamine, dimethyl hydantoin, guanidine, thiourea and the likealso can be included in amounts of 01-10%. There can even be includedcon- (e.g. 95:5), ethylene-propylene-cyclopentadiene terpolymer (e.g.:17:31) and the like.

EXAMPLE 1 1 mole (227 grams) of butyl stannoic acid was dehydrated in800 grams of benzene by azeotropic distillation. Most of the benzene wasdistilled off at reduced pressure. There was then added slowly withagitation 452 grams (2.21 moles) .of isooctyl mercaptoacetate to thedehydrated butyl stannoic acid at C. The removal of benzene and thewater of reaction was continued for three hours at reduced pressureafter all the isooctyl mercaptoacetate was added while holding thetemperature under 95 C. The product in the reaction flask afterfiltration was a water-white clear liquid.

1 1 EXAMPLE 2 Two moles (565.1 grams) of butyltin trichloride wasreacted with 12 moles (480 grams) of 50% sodium hydroxide in 2000 gramsof water by addition of the alkali to the solution of butyltintrichloride and water at 50 C., and after filtration, water washing theproduct to remove There was reacted 695 grams (1.96 moles on a drybasis) of the wet butyl stannoic acid and 428 grams (1.96 moles) ofisooctyl B-mercaptopropionate under reduced pressure at 70125 C. forfive hours with agitation. Upon filtration there was obtained thepolymeric tin ester as a clear, water-white liquid.

EXAMPLE 3 The procedure of Example 1 was repeated using 2.34 moles ofisooctyl p-mercaptopropionate in place of the isooctyl mercaptoacetateto produce the reaction product as a liquid.

EXAMPLE 4 The procedure of Example 2 was repeated replacing the isooctylmercaptopropionate by 1.96 moles of acetic acid to produce the polymericcondensation product of butyl stannoic acid with acetic acid as aninfusible solid.

EXAMPLE 5 The procedure of Example 2 was repeated replacing the isooctylmercaptopropionate by 1.96 moles of glycolic acid to produce thepolymeric condensation product of V butyl stannoic acid with glycolicacid as an infusible solid.

EXAMPLE 6 The procedure of Example 2 was repeated replacing the butylstannoic acid by 1.96 moles of octyl stannoic acid and replacing theisooctyl mercaptopropionate by 1.96 moles of mono butyl maleate toproduce the polymeric condensation product of octyl stannoic acid withmono butyl maleate as a liquid.

EXAMPLE 7 The procedure of Example 2 was repeated using as the reactants1.96 moles of phenyl stannoic acid and 1.96 moles of isooctylmercaptoacetate to produce the polymeric condensation product of phenylstannoic acid with isooctyl mercaptoacetate as a liquid.

EXAMPLE 8 The procedure of Example 1 was repeated using 2.34 moles ofglycolic acid in place of the isooctyl mercaptoacetate to produce thecorresponding reaction product.

EXAMPLE 9 EXAMPLE 10 A stabilized composition was prepared by mixing 2parts of the product prepared in Example 1 with 100 parts of polyvinylchloride (Geon 101EP).

EXAMPLE 1] A similarly stabilized resin was obtained by mixing 3 partsof the product prepared in Example 3 with 100 parts 12 of polyvinylchloride (Geon 101E?) and 50 parts of dioctyl phthalate.

EXAMPLE 12 A stabilized polyvinyl chloride composition was obtained byreplacing the tin stabilizer employed in Example 10 with 2 parts of thepolymeric tin ester prepared in Example 2.

EXAMPLE 13 Stabilized polyvinyl chloride compositions were also obtainedby replacing the tin stabilizer employed in Example 10 with (a) 2 partsof the tin ester prepared in Example 3; or (b) 2.5 parts of thepolymeric tin ester prepared in Example 4; or (c) 2 parts of thepolymeric tin ester prepared in Example 5; or (d) 2 parts of thepolymeric tin ester prepared in Example 6; or (e) 3 parts of thepolymeric tin ester prepared in Example 7: or (f) 2.5 parts of the tinester prepared in Example 8; or (g) 2 parts of the tin ester prepared inExample 9.

EXAMPLE 14 Compositions were prepared by adding to parts of polyvinylchloride (Geon 101-EP) and 0.25 part of mineral oil to the followingmaterials:

(a) 1.48 parts of polymeric monobutyltin mono isooctylB-mercaptopropionate oxide (the compound prepared in Example 2).

(b) 2.0 parts of the compound prepared by reacting one mol of dehydratedbutyl stannoic acid with 2.34 mols of isooctyl beta-mercaptopropionate(the compound prepared in Example 3).

(c) 2.6 parts of monobutyltin tris isooctyl fi-mercaptopropionate.

(cl) 1.17 parts of monobutyltin mono isooctyl thioglycolate.

(e) 1.9 parts of the compound prepared in Example 1.

(f) 2.6 parts of monobutyltin tris isooctyl thioglycolate.

(g) 2.0 parts of dibutyltin bis isooctyl thioglycolate.

The proportions of the different compounds in Example 16(a) through (g)where chosen so as to give equal quantities of tin metal in each case.

All the formulations were then heat aged at 350 F. for times up tominutes (2 hours).

Formulation 16(d) began to darken at 15 minutes and was completely blackat 75 minutes. Formulation 16(c) began to darken after 30 minutes andwas completely black after 120 minutes. Formulation 16(g) was a mediumbrown after 120 minutes and the poorest of the remaining samples.Formulation 16(f) was a very light brown after 120 minutes and was thenext poorest sample. The best sample was Formulation 16(c) which hadbarely changed color after 120 minutes. Formulation 16(a) and 16(b) weresubstantially identical in appearance after 120 minutes and wereintermediate between Formulation 16(c) and Formulation 16(f) inappearance.

In place of monobutyltin tris(isooctyl fi-mercaptopropionate) as astabilizer as set forth in Example 16(c) there can be used othermonohydrocarbyltin tris(hydrocarbyl fl-mercaptopropionate) where thehydrocarbyl groups are alkyl, aryl, or aralkyl such as mono butyltintris(Z-ethylhexyl B-mercaptopropion'ate), monobutyltin tris(octylB-mercaptopropionate), monobutyltin tris(butyl fl-mercaptopropionate),monobutyltin tris(decyl fi-mercaptopropionate), monobutyltintris(octadecyl fi-mer captopropinate), monobutyltin tris(phenyl,B-mercaptopropionate), monobutyltin tris(p-tolyl B-mercaptopropionate),monobutyltin tris(p-butylphenyl B-mercaptopropionate), monobutyltintris(benzyl B-mercaptopropionate), monobutyltin tris(methylfi-mercaptopropionate), monobutyltin isooctyl bis(deeyl[i-mercaptopropionate), monooctyltin tris(isooctylfi-mercaptopropionate), monooctyltin tris(dodecylfl-mercaptopropionate), monophenyltin tris- (hexyl fi-mercaptopropionatemonobenzyltin tris(isodecyl p-mercaptopropionate), monomethyltintris(dodecyl S-mercaptopropionate), monooctadecyltin tris(ethylfimercapto pro pionate) t What is claimed is:

1. A halogen containing resin selected from the' group consisting ofvinyl chloride homopolymers, vinyl chloride copolymers, vinylidenechloride homopolymers, vinylidene chloride copolymers, polyvinylbromide, polyvinyl fluoride and chlorinated polyethylene containing astabilizingly effective amount of the condensation product of 1 mol ofmonohydrocarbyl stannoic acid with (a) 1 or (b) 2 to 2.5 mols of acompound having a formula selected from the group consisting of I HO O C(CH) OH; HS(CH2) C O R1; HO 0 CR4; HOOC CH2)m COOR; and HOOCCH=CHCOORrwherein R is hydrogen or methyl, R is hydrocarbyl, R is hydrogen orhydrocarbyl, m is 0 or a positive integer and q is an integer of atleast 1.

2. A composition according to claim 1 wherein the resin is selected fromthe group consisting of chlorinecontaining vinyl and vinylidene resins.

3. A composition according to claim 1 wherein the resin is a vinylchloride resin.

4. A composition according to claim 1 wherein the halogen containingresin is a vinyl chloride resin and the condensation product is acondensation product of 1 mole of monobutyl stannoic acid with 1 mole ofoctyl-fi-mercaptopropionate.

5. A composition according to claim 4 wherein the octyl group isisooctyl.

6. A member of the group consisting of chlorine containing vinyl andvinylidene resins containing a stabilizingly effective amount of ahydrocarbyltin ester of a hydrocarbyl p-mercaptopropionate selected fromthe group consisting of (1) the polymeric condensation product ofequimolar amounts of a hydrocarbyl stannoic acid and a hydrocarbylbeta-mercaptopropionate and (2) the reaction product of 1 mole of ahydrocarbyl stannoic acid with 2 to 2.5 moles of hydrocarbylbeta-mercaptopropionate.

7. A composition according to claim 6 wherein said tin compound is saidreaction product of 1 mole of hy- 14 drocarbyl stannoic acid with 2 to2.5 moles of the mercaptopropionate.

8. A composition according to claim 1 wherein the tin ester is thepolymeric condensation product of equimolar amounts of a hydrocarbylstannoic acid and a hydrocarbyl fl-mercaptopropionate.

9. A vinyl chloride resin containing a stabilizingly effective amount ofa lower alkyltin ester of an alkyl )3- mercaptopropionate selected fromthe group consisting of the polymeric condensation product of equimolaramounts of a lower alkyl stannoic acid and an alkylfi-mercaptopropionate, and the reaction product of 1 mole of lower alkylstannoic acid with 2 to 2.5 moles of alkyl beta-mercaptopropionate.

10. A composition according to claim 9 wherein the tin compound is saidreaction product of 1 mole of lower alkyl stannoic acid with 2 to 2.5moles of alkyl beta-mercaptopropionate.

11. A composition according to claim 9 wherein the alkyl stannoic acidis butyl stannoic acid and the alkyl mercaptopropionate is octylmercaptopropionate.

12. A composition according to claim 11 wherein the octyl group isisooctyl.

13. A composition according to claim 9 wherein the tin ester is thepolymeric condensation product of equimolar amounts of a lower alkylstannoic acid and an alkyl fi-mercaptopropionate.

References Cited UNITED STATES PATENTS 2,731,482 1/ 1956 Stefl.

2,789,102 4/ 1957 Weinberg 26045.75 2,809,956 10/ 1957 Mack 26045.752,985,617 5/ 1961 Salyer 26045.7 3,015,644 1/ 1962 Leistner 260-45.753,063,963 11/1962 Wooten 260-4175 3,255,136 6/1966 Hecker 26023;3,296,289 1/ 1967 Closkey 260- .75; 3,297,629 1/ 1967 Kauder 260429.T

DONALD E. CZAJA, Primary Examiner.

V. P. HOKE, Assistant Examiner.

F- In the specification, column 12, lines 41, L5, 48, 5a

5% UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,L13,26 Dated November 26, 1968 Ingenuin Hechenbleikner; Raymond S. Dalterand Inventor(s) John F. Hussar It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

53, 5 and 56 all occurrences of "16" should read 'l SKENED AND SEALEDJUL 141970 65 Anest:

wmmrm E. sum, an.

Attesn'ng Officer

